Cycloalkyl alkylene and arylalkylene polyamines

ABSTRACT

NOVEL POLYAMINES ARE PREPARED IN KNOWN MANNER. THEY HAVE THE FORMULA   H-(NH-CH2-CYCLOHEXYLENE-CH2)Q-NH-((CH2)P-NH-CH2-CYCLO-   HEXYLENE-CH2-NH)M-((CH2)P-NH)Q&#39;&#39;-H   IN WHICH:   P REPRESENTS A WHOLE NUMBER OF FROM 1 TO 12, PREFERABLY FROM 2 TO 4, Q AND Q&#39;&#39; EQUAL 0 OR 1, M REPRESENTS A WHOLE NUMBER OF FROM 1 TO 10, PREFERABLY FROM 1 TO 2 (IF Q AND Q&#39;&#39; ARE 0) TO 4, THE LINKAGES OF THE RINGS ARE 1,3 AND/OR 1,4-LINKAGES, AND, OPTIONALLY, TO A SMALL EXTENT, ALSO 1,2-LINKAGES, AT LEAST HALF OF THE RINGS BEING CYCLO-ALIPHATIC, THE REST BEING AROMATIC. THE RINGS MAY ALSO BE SUBSTITUTED BY LOW MOLECULAR WEIGHT ALKYL GROUPS. THE POLYAMINES ARE SUITABLE, FOR EXAMPLE, AS MODIFICATION COMPONENTS FOR THE PREPARATION OF FILM AND FIBER-FORMING POLYAMIDES.

3,755,445 CY CLOALKYL-ALKYLENE- AND ARYLALKYLENE-POLYAMINES ErnstHanschke, Burghausen, Walter Fester, Konigstein,

United States Patent 01 lice 3,755,445 Patented Aug. 28, 1973 in which:

p represents a whole number of from 1 to 12, preferably from 2 to 4, qand q' equal or 1,

Taunus, and Franz Jakob, Hofheim, Taunns, Ger- 5 m represents a wholenumber of from 1 to 10, preferably many, assignors to Farbwerke HoechstAktiengesellfrom 1 or 2 (if q and q are 0) to 4, fi fi g gg g Lucius &Bmmng Frankfurt the linkages of the rings preferably being 1,3- and 1,4-No nmwfing Filed 19, 1970 sen 65,298, linkages, and in which at leasthalf of the rings are cyclo- Claims priority, application Germany, Aug.26, 1969, allphatlethe l'est belllg afomatle- P 19 43 254.3 Preferenceis given to those polyamines of the above- Int. Cl. C07c 87/02, 87/28mentioned structure which have exclusively cyclo-ali- US. Cl. 260-563 R2 Claims phatic rings or cycle-aliphatic and aromatic rings in analternating sequence.

These polyamines exhibit a very good thermostability. ABSTRACT OF THEDISCLOSURE They do not decompose, nor do they show any discolora- Novelpolyamines are prepared in known manner. tion, even if heated for sometime at 200 C. and more, They have the formula whereas the correspondingpolyamines containing exclu- H HN-CH; CHlNH (CHz)n-NHCHz CH:NH (CH2)pNHH lo I- Im a in which: sively aromatic rings in the molecular chains,instead of p represents a whole number of from 1 to 12, preferablycyclo'ailpham i aromatlc Show a brown from 2 to 4, colorat on and signsof decomposition alreadyafter a very q and equal 0 or 1, short time, ifheated at 200 C. The stab lizing eifectof m represents a whole number offrom 1 to 10, preferably cyclo'ahphatlc. p m t correspondmg polyanflmefrom 1 or 2 (if q and are 0) to 4, 3O molecular chains is surpnsrng andhas not been described so far. The polyamines in accordance with theinvention thelinkages 0f the rings are and/01 l ,4-liflkeges, and, areadvantageously prepared While using as starting com- P y, to a SmalleXteIlt, also g at least pound hydrogenated xylylene diamine or amixture of at half of the rings being W p the fest being least 50 molpercent of hydrogenated xylylene diamine matic. The rings may also besubstituted by low molecular and nomhydmgenated xylylene diamine and ihl Welght alkyl p The polyamines are Suitable, for alkanes of theformula Cl(CH Cl (p representing a ample, as modification components forthe preparation of h l number f from 1 to 12, f bl fro 2 t 4), film andfiber-forming p lyamides. optionally in the presence of NH, (if themolar ratio of hydrogenated/non-hydrogenated xylylene diamine to di- Thepresent invention relates to novel polyamines and 40 chloralkane.is 1:1)the preparation being eflected to a process for preparing themcordancewith processes that are common for reactions Canadian Pat. No.837,201 describes a process for the of thls Hydrogenated or Lil-xylylenepreparation of polyamines by means of desaminating hyas .well asmlxtures of hydrogenated .xylylene d1- drogenation of xylylenediamine(s), in which process f are used as hydrogenated xylylene mpolyamines are formed, in the molecule chains of which mg comp.ounds'Hydrogenated ofiylylene dlamme 18 less the six-membered ringsoriginating from xylylene diamine sultabhi'; It can g P m small f z areall hydrogenated, i.e. cycle-aliphatic. These polya maxlimum 12 imixture Wlth hy roamines are distinguished by a remarkablethermostability gepate 39 'Xyly ene dlamme' What has p which makes themsuitable for numerous application purabout e Homers of hydrogenatedxylylene d1. poses, for example for the modification of film andfiberamme Startmg compoupd al-so-true for the nonhydFo formingpolyamides and as hardeners for epoxide resins. genated xylylen? dlammeIf ls used as S-tarm-lg The said polyamines have the formula compound.If, 1n the preparation of the polyamines 1n accordance with theinvention, no unlform hydrogenated (and non-hydrogenated) xylylenediamine isomer is used HZN OH (H) CH as starting compound, the linkagesof the ring of the final V I product are, naturally, not uniform either,but consist of 1,3-, 1,4- and, optionally, 1,2-linkages. It is alsopossible to use, instead of a uniform dichloralkane, a mixture of L l mA two or several diehloralkanes falling under the above gen- NHCH:(H)OHNHCH -(H)--OH NH eral formula Cl(CH Cl (with diflerent values for p).

L V L V Furthermore, it is possible to use, instead of the unsubstitutedhydrogenated and non-hydrogenated xylylene diin which x equals 0 or awhole number of from 1 to 30, amines, hydrogenated and non-hydrogenatedxylylene dipreferably from 0 to 10, and in which the linkages of theamines that have been substituted preferably by low rings are preferably1,3- and 1,4-linkages. molecular weight alkyl groups having from 1 to 5carbon The present invention provides novel polyamines of the formulaatoms. In this case, the polyamines obtained have (alkyl-) substitutedcyclohexane and benzene rings in the molecular chains, instead of theunsubstituted rings in the formula for the polyamines according to theinvention.

The polyamines of the invention can also be prepared in a difierentmanner, for example by means of desaminating hydrogenation of xylylenediamine(s) and the corresponding diaminoalkanes of the formula (prepresenting a whole number of from 1 to 12, preferably from 2 to 4) atan elevated temperature and an increased hydrogen pressure, while usingpreferably a nickel catalyst containing other heavy metals. If in thisprocess polyamines are to be obtained which contain, besidescyclo-aliphatic rings, also aromatic rings in the molecule chains, thereaction has to be stopped before the amount of H necessary for thecomplete hydrogenation of the aromatic nuclei of xylene has beenabsorbed. If the reaction is stopped after half the amount of Hnecessary for the complete hydrogenation has been absorbed, polyaminesare obtained which have cyclo-aliphatic and aromatic rings in themolecular chains in the same ratio.

The polyamines of the invention are colourless, or at the most slightlyyellow, completely liquid substances, which are suitable, for example,as modification components for the preparation of film and fiber-formingmodified polyamides in accordance with US. patent application Ser. No.65,300 filed concurrently herewith and entitled Fiber-Forming PolyamidesWith an Increased Content of Amino Groups and now U .S. Pat. No.3,711,447 issued on Jan. 16, 1973.

The following examples serve to illustrate the invention.

EXAMPLES (1) A mixture was prepared consisting of 3 moles of a mixtureof hexahydroxylylene diamine isomers (1,3-:1,4 hexahydroxylylene diamine7:3) and the amount of aqueous sodium hydroxide solution of 40-50%strength calculated on 1 mole of ethylene chloride, the mixture washeated with reflux to about 100 C., while 1 mole of ethylene chloridewas dropped in, and was then kept for another hour at about 100 *0.Subsequently the water was removed by means of azeotropic distillationwith xylene, the residue was freed from NaCl by suction, and xylene aswell as the excess of the starting diamine "were distilled 01f in vacuo.The residue, which was prac- A polyamine prepared in analogous manner onthe basis of 3 moles of a mixture of non-hydrogenated xylylene diamineisomers (ratio of mto p-xylylene diamine 7:3) and 1 mole of ethylenechloride (yield: 81.5%, amine number 127, nitrogen content: 17.7%)resinified in the thermal test at temperatures over 200 C., whilesplitting off ammonia and showing a brown discoloration.

What is claimed is:

1. A polyamine of the formula wherein A represents cyclohexylene orphenylene, at least half of the As are cyclohexylene groups; prepresents a whole number from 1 to 4; q and q equals 0 or 1; mrepresents a whole number from 2 to 4 when q and q are 0 and 1 to 4 whenq and q are greater than 0.

2. A polyamine as defined in claim 1 having only cyclohexylene groups inthe molecular chain.

References Cited UNITED STATES PATENTS 2,519,440 8/1950 Benneville etal. 260570.9 X 3,196,180 7/1965 Albert 260570.5 3,351,650 11/1967 Crosset a1 2605 63 X OTHER REFERENCES Teshiro et al.: Chemical Abstracts,vol. 67, 729461;, p. 6853 (1967).

ROBERT V. HINES, Primary Examiner U.S. Cl. XJR.

26078 R, 78 TF, 570.5 P, 570.9

